US3429870A - Reactive triazine containing azo dyestuffs - Google Patents

Description

United States Patent 3,429,870 REACTIVE TRIAZINE CONTAINING AZO DYESTUFFS Luigi Carati, Milan, Ugo Moiso, Cesano Maderno, and

Giulio Craia, Saronno, Italy, assignors to Aziende Colori Nazionali Aflini ACNA S.p.A., Milan, Italy No Drawing. Filed Aug. 6, 1965, Ser. No. 477,931

Claims priority, application Italy, Aug. 10, 1964 17,310/ 64 US. Cl. 260-153 Int. Cl. C09b 62/50, 29/38, 29/16 8 Claims ABSTRACT OF THE DISCLOSURE Dyestuffs for dyeing cellulose and polyamide having the general formula I Cl where n=2, 3 or 4 and the chromogen is a residue of azo, metallized azo, anthraquinone or phthalocyanine dyestutf. Foregoing dyestufls prepared by reacting cyanuric chloride with Na salt of N'-methyl-sulfanilamido-methanesulfonic acid and then condensing the product with the dyestufi" residue. Textile materials dyed with foregoing dyestulfs.

The present invention relates to a new class of reactive triazine dyestuffs which are particularly suitable to obtain dyeings having a high fastness to wet treatments on cellulose and polyamide materials.

Previously, a class of reactive dyestuffs of the general formula where n=2 or 3, and wherein the chromogen was selected from the group consisting of azo dyestuif, azo metallized dyestufi and anthraquinone dyestufi', has been disclosed.

It has now been surprisingly found that the dyestufis to the general formula '(SOaNah N N CH5 where n=2 4 and wherein the chromogen radical -H SON CHgSO Na is bound to a carbon atom of the triazinyl nucleus, due to its controlled afiinity, is more uniformly distributed in the fiber and is fixed to it by means of a physical or chemophysical bond. Consequently, the dyestutf is in the most suitable condition to react with the fiber to a high degree, at the same time causing an excellent exhaustion of the bath.

(2) The dyestutt not chemically fixed on the fiber is quantitatively removed owing to its good dilfusion-deriving from the aflinity and solubility which it possesses to the most suitable degree-by subsequent soaping at the boiling temperature, thus allowing one to obtain high fastness to wet treatments.

The reactive dyestuffs of the general Formula II can be prepared by reacting cyanuric chloride with the sodium salt of N'-methyl-sulfanilamido-methanesulfonic acid and subsequently condensing the condensation product obtained with a chromogenic residue of a dyestuif selected from the group consisting of azo dyestutf, metallized azo dyestutf, anthraquinone dyestufi and phthalocyanine dyestulf.

They may also be prepared by condensing the chromogenic part (such as an azo, a metallized azo, an anthraquinone or phthalocyanine dyestutf) with the sodium salt of N'-methyl-sulfanilamido-methanesulfonic acid.

The dyestufis of the present invention are suitable both for dyeing and for printing many types of materials, such as natural and synthetic polyamides, wool, silk, superpolyamides, and are particularly efficacious for polyhydroxylated materials having a fibrous structure, such as regenerated cellulose, flax, and cotton.

The dyeing and printing of cellulose materials and natural and synthetic polyamides with the dyestuffs of the present invention are substantially carried out according to known techniques.

The parts and percentages, except when otherwise indicated, are to be understood as being expressed by weight.

EXAMPLE 1 49 parts by volume of an aqueous solution of monomethylamine having a concentration of 31.8% parts/vol. are dropwise added to 300 parts by volume of a solution of sodium oxymethanesulphonate having a concentration of 35.5% parts/vol. in 3 hours at 55-60 C., while keeping the pH between 7.58.5 by means of suitable regulation of the dropping of the methylarnine. To the thus obtained reaction mixture, 245 parts of N-p-acetyl-aminobenzene-sulphonylchloride, having a concentration of 47.8% are added.

The pH is kept at a value of 6.5-7 for 10 hours by means of addition of 425 parts by volume of a solution of Na CO having a concentration of 10% parts/vol. When constant pH values of 6.5-7 are reached, the mixture is filtered and 200 parts of rock salt are added to the filtrate at room temperature. It is then stirred for 2 hours and then the sodium salt of N-p-acetyl-amino-benzene-sulphonamido-N-methyl-N omega methane sulphonic acid is filtered and subsequently washed on the filter with a solution of purified rock salt.

The aqueous paste obtained, having an ivory-white color, is subsequently added to a solution of 40 parts/vol. of concentrated HCl in 350 parts of water. The whole is maintained at about 60 C. for 7 hours; then it is filtered at room temperature and washed with water until the chlorides are removed. The paste cake is dried on CaC1 A white powder, which under analysis reveals the chemical structure of N-methyl-sulfanilamide-methanesulfonic acid, is obtained with good yields.

EXAMPLE 2 9.22 parts (0.05 g.-mol) of cyanuric chloride in 50 parts of acetone are poured in a thin trickle onto 80 parts of ice and 80 parts of water; after 2-3 minutes of stirring, and while keeping the temperature below 3 C. by means of suitable and gradual additions of finely ground ice, the solution, at pH 6.5, of 14.0 parts (0.05 g.-mol) of N'-methyl-sulfanilamido-methanesulfonic acid, prepared as described in Example 1 (M.P. 280.3) in 150 parts of water of about 18 C. and 3.5 parts of Na CO is charged in 15 minutes; the pH of the milky suspension is kept between 6.0 and 6.5 by means of gradual dropping of 25-26 parts by volume of an aqueous Na CO solution having a concentration of 10% parts/vol.

After 1 to 1.5 hours of stirring at 2-3 C., when the pH is stabilized and the diazotizable amine group has disappeared, the solution, having a pH of 7 obtained by dissolving with NaOH the coupling product (in acetate medium) of the diazo of 15.1 parts (0.05 g.-mol) of 2- naphthylamine-4,8-disulphonic acid with 9.33 parts (0.05 g.-mol) of 3-amino-acetanilide hydrochloride, is introduced. The whole is heated to about 40 C. in 30 minutes and the condensation solution is kept at this temperature for hours, while constantly bringing the pH back to 6.5 by means of gradual addition of 25-26 parts by volume of an Na CO solution having a concentration of 10%.

After filtration to remove occasional mechanical impurities, the solution is salted out with NaCl in order to precipitate the dyestufi.

S03Na NH l c 000113 I SOaNa C1 amido-methanesulfonic acid in 150 parts of water at about 18 C. and 3.5 parts of Na CO by means of gradual dropping of 25-26 parts by volume of an aqueous Na C0 solution having a concentration of 10% parts/ vol. the pH of the milky suspension is maintained between 6.0 and 6.5.

After 1 to 1.5 hours of stirring at 2-3 C., when the pH is stabilized and the diazotizable amine group disappeared, 9.4 parts (0.05 g.-mol) of 2,4-diaminobenzenesulphonic acid, previously solubilized in 100 parts of water, are added and the whole is heated to about C. in 1 hour.

After 1 to 1.5 hours of stirring at this temperature, always keeping the pH of the condensation solution between 6.0 and 6.5 by means of gradual addition of 25- 26 parts by volume of an Na CO solution having a concentration of 10%, the stabilization of the pH occurs.

After filtering ofi occasional mechanical impurities the condensation solution is cooled at 0-3 C. and first 3.45 parts of NaNO,, (in the form of an aqueous solution having a concentration of 23% parts/vol.) and then 14.7 parts of HCl, sp. p. 0 =1.175 are added to it; after 20 minutes of stirring at 0-3 C. the suspension of the diazo compound is charged in 15 minutes into the solution at 20 C. of 16.6 parts (0.515 g.-mol) of l(2,5-dichloro-4-sulfophenyl)-3-methy1-5-pyraz0lene in 140 parts of water and 15 parts of Na C0 It is left under stirring until the diazo compound has disappeared.

The dyestufr'.

SOaNa HaCO-CN=N i 0-0]: CIIHZ \N/ Nn( (l.?NH-S0zN-CHzSOaNa N /N or o SOaNa which is then filtered under vacuum-leaving it to dry as is precipitated by salting out with KCl, filtered under much as possibleand finally dried in an oven at about vacuum-leaving it to dry as much as possibleand 35-40 C. for hours. finally dried in an oven at about 35-40 C. for 60 hours.

When dissolved in water it gives an orange yellow solu- Said dyestufif, when dissolved in water, gives a lemon tion, which dyes, with excellent exhaustion, cotton in a 60 yellow solution and dyes, with excellent exhaustion, cotreddish yellow shade with good fastness after alkaline ton in a greenish yellow shade with good fastness after thermofixing. alkaline thermofixing.

The same dyestuif is obtained when carrying out the The same dyestuff is obtained when carrying out the condensation in the opposite sense, i.e., by condensing condensation in the opposite sense, i.e., when condensing with cyanuric chloride first the monoazo compound and with eyanuric chloride first the 2.4 diarnino benzenesulthen the N'methyl-sulfanilamido-methanesulfonic acid. fonic acid and then the N'-rnethyl-sulfanilamido-methane- EXAMPLE 3 sulfomc acid.

9.22 parts (0.05 g.-mol) of cyanuric chloride in 50 EXAMPLE 4 parts of acetone are poured in a thin trickle onto 80 parts 0f ice a 30 Pf Of Water; after minutes of Stirring The suspension of the diazo compound prepared as and Whlle keplflg the temperature below y means described in Example 3 is charged in 15 minutes into of suitable and gradual addition of finely ground ice, it is the solutionof 21.8 parts (0.515 g.-mol) of 1. b i added in 15 minutes to the solution, having a pH of 8-naphthol-3,6-disulphonic acid in 250 parts of water and 26.5, of 14.0 parts (0.05 g.-mol) of N'-methyl-sulfanil- 7 15 parts of Na CO kept at 20 C.

6 After coupling the pH is brought to 7 by means of addi- EXAMPLE 6 tion of HCl and the dyestuii 57.8 parts (0.1 g.-mol) of the monoazo compound ob- (JO-NH OH SOaNa 11 N=N N CH;

Na0aS SOJNB- NHC G-NH- SOzN-CH:S OgNa II II N\ /N is precipitated by salting out with KCl, filtered under tained by alkaline coupling (pH 8.5-9) of the diazo comvacuumleaving it to dry as much as possibleand finalpound of l-amino-Z-naphthol 6-nitro-4-sulphonic acid ly dried in an oven at about 3540 C. for 60 hours. with Z-amino-S-naphthol 7-sulph0nic acid, are suspended Said dyestulf, when dissolved in water, gives a bluish in 250 parts of water at 50 C. and an aqueous cobalt red solution which dyes, with excellent exhaustion, cotton sulphate solution is added under stirring to them so as in a red shade having good fastness after alkaline thermoto reach a ratio of 0.055 gram atoms of cobalt per 0.1 fixing. g. mol of monoazo compound; the suspension is metal- The same dyestufi is obtained when carrying out the lized at 70 C. in 1 to 1.5 hours at a pH of 6-6.5, while condensation in the opposite sense, i.e., when condensing maintaining said pH by means of addition of caustic soda with cyanuric chloride first the 2.4-diaminobenzenesulfon- 5 N. ic acid and then the sulfanilamido-N'-methyl methanesul- The obtained solution is filtered, cooled at room temf ie acid, perature (about 20 C.) and added to the mono-con- EXAMPLE 5 densate suspension of cyanuric chloride and sodium sulphanyl-amido-N'-methyl-N'-methanesulphonate, prepared The suspension of the diazo compound prepared acas described be1ow: cording to mple 3 is charg d in 0 minutes int a A solution of 22.2 parts of cyanuric chloride (M.W. So ut on of Parts 0f arbamyliso- 184.4) in 140 parts of acetone is poured onto 60 parts gamma acid in 180 part f W e having P p v of ice, 60 parts of cold water and 1-2 drops of Emulgator ously salted to a concentration of 10% parts/vol. with (MK) (in solution having a concentration of 5%); 0.12 NaCl and cooled to about 2-3" C.; contemporaneously g.-mol of the sodium salt of N'-methy1-sul-fanilamidowith the addition of the diazo compound about 65 parts 40 m thanesulfonic acid (M.W. 280.3) in 300 parts of cold b l me of an aqueous solution of Na CO having a water are then added to the suspension obtained. concentration of 10% parts/vol. are dropwise added in The whole is stirred for 1.5 hours at a temperature of order to maintain the pH constant between 7.0 and 7.5. 0 5 C. and at a pH kept at 6-6.5 by dropwise addition The Whole is left under stirring at about 23 C. until of an Na CO solution having a concentration of 10% the diazo compound has disappeared. parts/vol. until a negative reaction of the diazotization The obtained dyestulf havmg the structure sample is reached.

( 11 5 OaNB N CH3 I I SOaNi Nil-(l3 (fi-NH 802-171 0 0 N N CH:

l l NH: 0 SOzNa is filtered under vacuum, washed with brine having a The mixture contzilining the suspensifm of the monoconcentration of 10% left to dry as much as Possible condensate thus obtained and the solution of the metaland finally dried in an oven at 3540, vfor 60 houm 11z ed monoazo compound, is heated to 40 C. and kept at When dissolved in water said dyestuff gives an orange Said temperature for abPut 2 hours; the 15 Prought solution which dyes, with excellent exhaustion, cotton in to and f 331d Yalue by P addltioll of an orange Shade having good fastness after alkaline an Na CO solution having a concentration of 10% thermofixing. (P

The same dyestufi is obtained when the condensation It is left to 6001 under Stirring at room temperature is carried out in the opposite sense, i.e., when condensing and salted out at a concentration of with cyanuric chloride first the 2,4-diaminobenzenesulfon- 15% (par-ts/ vol.) with NaCl. Then it is filtered and dried ic acid and then the N'-methyl-sulfanilamido-methaneat After g g a rk, highly soluble powder sulfonic acid. is obtained having the structure:

which dyes cellulose fibers in a violet brown shade having a good substantivity and reactivity.

EXAMPLE 7 57.8 parts of the monoazo compound obtained by alkaline coupling (pH 8.5-9) of the diazo compound of l-amino-2-naphthol-6-nitro-4-sulphonic acid with 2-amino-5- naphthol-7-sulphonic acid, are suspended in 250 parts of water at 50-60 C. and a solution of sodium-chromiumsalicylate, having a concentration of 2.6% of Cr (prepared according to known modalities) is added thereto so as to reach a ratio of 0.08 gram atoms of Cr per 0.1 mol of monoazo compound; the metallization is carried out at the boiling temperature, in a period of 2-3 hours and at a pH of 10.5-10.6, obtained by means of suitable additions of caustic soda (about N).

The resulting solution is filtered cooled at C. neutralized at a pH of 7 and added to the suspension of the monocondensate between cyanuric chloride and sodium N'-methyl-sulfani1amido-methanesulfonate, the preparation of which was described in Example 2 or 6.

The resulting mass is heated to 40 C. and kept at said temperature for about 2 hours; the pH is brought to 6.5-7 and is kept at said value by dropwise adding an Na CO solution having a concentration of 10% (parts/vol).

The whole is left to cool under stirring at room temperature (about 20 C.), and salted out at a concentration of 20% (parts/ vol.) with NaCl and the pH is brought to 4 with HCl 1:1.

The precipitate obtained is filtered and dried at 40 C. After grinding a dyestutt' is obtained in the form of a black powder having the structure:

OzN

which dyes, with excellent reactivity, cellulose fibers in SOsNa greenish grey shades having good fastness characteristics, excellent exhaustion of the dyeing bath.

EXAMPLE 8 Z-amino-1,4-benzenedisulfonic acid is directly diazotized and coupled with p-cresidine in a sodium acetate buttered medium. The amino-azo compound is diazotized and coupled with 2-amino-5-naphthol-7-sulphonic acid in an alkaline medium.

The diazo compound obtained, is transformed into its copper complex by heating it for 20 hours at C. with an aqueous solution of ammoniacal copper sulphate.

After cooling, the copper complex of the diazo compound is precipitated by salting out at a concentration of 20% (parts/vol.) with NaCl, at pH of about 4, and separated by filtration.

76.5 parts of the tri-sodium salt of the metallized diazo compound (M.W. 765) are dissolved in 500 parts of hot water by neutralizing at a pH of 7 with 5 N caustic soda, and added to the suspension of 0.12 mol of the monocondensate between cyanuric chloride and sodium N'-methylsulfanilamido-methanesulfonate, the preparation of which was described in Examples 2 and 6.

The resulting mass is heated to 40 C. and kept at said temperature for 2 to 3 hours; during said period the pH is brought to 6.5-7 and kept at said value by means of dropwise addition of Na CO solution having a concentration of 10% (parts/vol).

The whole is left to cool at room temperature (about 20 C.).

SOaNa SOaNa The dyestutf is separated by means of salting out at a 3,429,870 9 concentration of (parts/vol.) and at a pH of 4, and 0-5 C. and a pH of 6-6.5, maintained by means of addifiltration. After drying at 40 C. and grinding a blue powtion of Na Co until a negative reaction of the diazoder is obtained having the structure: tization test is reached.

SOaNB O-Cu0 E1 Q I N cm H: Naots Nari dun-Q-sm-i: \N% (3H SOaNa SOaNa which dyes cellulose fibers in a navy greenish blue shade A solution of 95 parts of the intermediate of the followwith good substantivity and reactivity. ing structure EXAMPLE 8 N I 9 I 2 03 3)! NH:

4-amino-azo-henzene-3,4-d1sulphon1c acid is dlazog tized indirectly at 20 C. and coupled with l-amino-naph- SOZNH thalene-6-sulphonic acid in a medium buffered with sodium acetate. Pc=nucleus of copper phthalocyanine in 2000 parts of The diazo compound obtained is separated by means water are added to this solution. of salting out and filtration. The mixture obtained is left under stirring at 20-25 C.

59 parts of the previously prepared amino-diazo comfor about 12 hours, while the pH is maintained at 6.5-7.5 pound (M.W. 591) are suspended in 600-700 parts of by means of suitable additon of NaHCO water and neutralized at a pH of 7 with a 1:1 NaOH When the condensation is completed a dyestuif is sepasolution. rated by salting out, having the structure The resulting solution is added to the suspension obtained by pouring the solution of 18.5 parts of cyanuric o1 chloride in 140 parts of acetone onto 50 parts of water, 50 parts of ice and 1-2 drops of Emulgator MK (CH -(CH CH SO Na, n=about 9-13 (some): a

NH- NH The whole is kept under stirring at 05 C. for 1 hour and at a pH of about 6 by addition of Na CO in solution SOZNH N having a concentration of 10% (parts/vol.) The solution,

at pH of 7, of 33.6 parts of the sodium salt of N'-methyl- 40 sulfanilamido-methanesulfonic acid (M.W. 280) in 300 parts of water is added to the solution obtained.

The solution is heated to 40 C. and kept for 4 hours at this temperature and at a pH of 6.5-7 by means of drop- N CH ping of an Na CO solution having a concentration 10% H1 (parts/vol). It is left to cool at room temperature, salted 303m out at a concentration of 20% (parts/vol.) and filtered.

The drying is carried out at 40 C. which dyes cellulose fibers, in the presence of acid-bind- After grinding a dyestufi is obtained in the form of a ing substances, in a turquoise shade having excellent fastbrown powder having the structure: ness characteristics.

SOzNa N N (EH: NaOaS-N=NN=N NH-b iB-NH-Q-SWN I N CH:

SO|Na which dyes cellulose fibers in a yellowish-brown shade 5 EXAMPLE 11 with good substantivity and reactivity.

EXAMPLE 10 By operatmg as described in the preceding example, but

using the intermediate having the following structure A solution of 22.2 parts of cyanuric chloride in 140 so H parts of acetone is poured into a mixture of parts of ice g a NH: and 60 parts of water. PO-SOZNH! l A milky suspension is obtained to which a solution of 33.6 parts of the sodium salt of N'-methyl-sulfanilamidomethanesulfonic acid in 300 parts of cold water is added.

The whole is stirred for 1.5 hours at a temperature of a dyestufi having similar characteristics is obtained.

1 1 EXAMPLE 12 By operating as described in Example 10, but using the intermediate having the following structure a dyestulf having analogous dyeing characteristics is obtained.

EXAMPLE 13 S OaNa I 0 NHQSOaNa i SOaNa SOaNa In the presence of acid-binding substances it dyes cellu- 70 lose fibers in shades very fast to wet treatments.

EXAMPLE 14 By operating as described in the preceding example, but using as intermediate the 1-amino-4-(3'-amino- 7 anilino)-2-anthraquinonesulphonic acid, a dyestufi' is obtained which has the following structure:

and which dyes in a deeper red shade than the dyestufi obtained according to Example 14.

EXAMPLE 15 The solution obtained by coupling at 3-5 C. and at a pH of about 9 the diazo of 18.9 parts (0.1 g.-mol) of the Z-amino-l-phenol-4-sulphonic acid with 31.9 parts (0.1 g.-mol) of H acid was copper metallized at 40 C. and at a pH 5 (using as bufiering agent 27.5 parts of crystallized sodium acetate) with parts (0.1 g-mol) of CuSO -5H O; after one hour at 40 C. the solution was salted ofi to 20% parts/vol. with NaCl and the whole was filtered off at 20 C.

The solution of the copper metallized monoazo thus obtained having a pH=7 (26.2 parts corresponding to 0.045 g.-mol in 200 ml. of water) is poured on the condensation product of 0.05 g.-mol of cyanuric chloride and 0.05 g.-mol of N-methyl-sulfanilamido-methanesulfonic acid (prepared according to modalities described in Example 2). The solution, heated Within minutes at about C., is kept at this temperature for 3 hours maintaining the pH at the constant value of 6.5 by addition of a 10% Na CO solution.

The solution is then made clear and then is salted off with KCl in order to precipitate the dyestufi haustion and good fastness after alkaline heat treatment.

The same dyestufi is obtained by carrying out the condensations in the opposite sense, that is condensing with 13 14 the cyanuric chloride first the copper metallized monoazo The condensation mass is heated at about 40 C. within f i n the N'-!I1ethY1-S111fa1111amid0 methane-8111mm: 30 minutes and is kept at this temperature for 6 hours, acl while maintaining the pH at the constant value of 6.5

EXAMPLE by gradual addition of a 10% Na CO solution.

The hydrolyzed and neutralized at pH 7 solution of the 5 The whole is salted off with NaCl having been made product obtained by coupling at 3 C. and pH 8-8.5 of clear, the thus precipitated dyestufi:

0.04 g.-mol of acetyl H acid (successively hydrolyzed with 4% NaOH) is Poured 011 the Condensation Product is filtered under vacuum and is then dried at about 3540 of 0.05 g.-mol of cyanuric chloride with 0.05 g.-mo1 of N'-methyl-sulfani.lamido methanesulfonic acid (prepared according to the modalities described in Example 2) Th1s dyestufl dlssolves in water and gives an intensively The whole is heated at about C Within minutes colored violet-reddish solution which dyes cotton in rubine and the condensation mass is kept at this temperature shade with good exhaustion and good fastness after alkafor 6 hours, while maintaining the pH at the constant 25 line heat trealimentvalue of 6.5 by gradual addition of a 10% Na CO solu- The same dyestufl? is obtained condensing the cyanuric fiO chloride first with the copper metallized monoazo and The Solution is 1 4 clear and then is salted ofi with then the N-methyl-sulfanilamido-methanesulfonic acid. NaCl; the thus precipitated dyestufi N SOaNa 0H NHC C-NH- SOa-N-OHaSOaNa I I II A N N Ha N=N NaOaS G1 SOaNa is filtered under vacuum and then is dried at about 40 EXAMPLE 18 C, The solution at pH 7 of 12 parts (0.05 g.-m0l) of 1- This dyestufi is water soluble and gives a red-bluish naphthol-6-arnino-3-sulphonic acid in 200 parts of water solution which dyes cotton in red-bluish shade with very is poured on the condensation product of 0.05 g.-mol of good exhaustion and good iastness after alkaline heat cyanuric chloride with 0.05 g.-mol of N-methyl-sulfani1- treatment, 5 amido-methanesulfonic acid, prepared according to the The same dyestuif is obtained by carrying out the conmodalities described in the Example 2. densations in the opposite sense, that is first condensing The whole is heated at 40 C. within one hour and is the cyanuric chloride with the hydrolyzed monoazo, and kept at this temperature for one hour and 30 minutes, then the N'-methy1-sulfanilamido-methanesulfonic acid. While the pH of the condensation solution is kept con- EXAMPLE 17 stant at a value between 6 and 6.5 by gradual addition of a 10% Na CO solution; after the stabilization of the The solution obtained by coupling at 3-5 C. and pH pH and after the disappearing of the diazo-table amino 9-9.2 the diazo of 18.9 parts (0.1 g.-mol) of the Z-aminogroup, the solution of the dicondensation product is 1-phenol-4-sulphonic acid with 23.9 parts (0.1 g.-mol) cooled at 3-5 C. and at this temperature the diazo of of the l-naphthol-6-amino-3-sulphonic acid was copper 11.5 parts (0.05 g.-mo1) of 4-acetoamino-2-sulpho-aniline, metallized at 65 C. and at pH 5 (using as buffering is poured unto it while the pH of the copulation mass is agent 27 parts of crystallized sodium acetate) with 25 maintained between 7 and 8 by gradual addition of a parts (0.1 g.-mol) of CuSO -5H O; after 23 hours at 10% solution of Na CO 60-65 C. the whole was cooled at about 20 C. and then After salting OE With NaCl, the dyestuflf thus precipitated SOzN8 0H (0'11 HaC-CO-NH- N=N N N H3 was salted off to 10% with NaCl and filtered. 0.04 g.-mol

of the copper metallized monoazo thus obtained after is filtered under vacuum and then is dried at about solubilization with 400 parts of water, are poured on the 9 condensation product of 0.05 g.-mol of cyanuric chloride Th1s dyestufi fhSSOlVeS 111 and g es a brllhant i Q05 1 f Numethyl-su1fani1amido methanered solution WhlCh dyes cotton m a scarlet shade with sulfonic acid (prepared according to the modalities degood exhaustion and with good fastness after alkaline heat scribed in Example 2). treatment.

EXAMPLE 19 The solution, obtained by coupling the diazo of 13.7 parts (0.1 g.mol) of anthranilic acid with 23.9 parts (0.1 g.-mol) of 1-naphthol-6-amino-3-sulphonic acid at a pH between 8 and 8.5, was copper metallized with 25 parts (0.1 g.mol) of CuSO -H O and 27.5 parts of crystallized sodium acetate; after one hour at 40 C. the whole filtered off.

0.05 g.-mol of the copper metallized monoazo thus obtained are added to the condensation product of 0.05 g.- mol of cyanuric chloride with 0.05 g.-mol of N-methylsulfanilamido-methanesulfonic acid (prepared according to the modalities described in the Example 2).

The condensation mass is heated at about 40 C. within 30 minutes and is maintained at this temperature till the condensation is complete, while the pH is continuously adjusted at the value of 6.5 by gradual addition of a Na CO solution.

After salting off with NaCl, the thus precipitated dyestuff is filtered under vacuum and then dried at about 35-40" C.

This dyestutf dissolves in water and gives a brownreddish solution which dyes cotton in a brown shade with good exhaustion and good fastness after alkaline heat treatment.

The same dyestuir' is obtained by condensing with the cyanuric chloride first the N'-methyl-sulfanilamido-methanesulfonic acid and then the 1-naphthol-6-amino-3- sulphonic acid, coupling then on this dicondensation product the diazo of the anthranilic acid at 3-5 C. and at a pH comprised between 7.58 and finally carrying out the copper metallization with CuSO -5H O at about 40 C. and at a pH=5.

EXAMPLE 2 parts of the dyestufi of Example 10 are dissolved in 100 parts of water.

With this solution a cotton fabric is impregnated, then squeezed until it retains 75% of its weight in solution, whereafter it is treated for 10 minutes at 75 C. in a bath containing 5-10 g./l. of trisodium phosphate, 1 ml./l. of NaOH 36 B. and 200 g./l. of NaCl.

It is rinsed in the cold, then at boiling temperature and then dried.

The cotton fabric appears to be dyed in a brilliant turquoise blue shade having good fastness.

EXAMPLE 21 parts of the dyestuff prepared according to Example 2 are dissolved in 1000 parts of distilled water.

With said solution a dry fabric of cellulose fiber is impregnated, then squeezed until it retains 75 of its weight of solution; the fabric is then dried at 70-80 C. and subsequently impregnated in a thus composed solution:

25% (parts/vol.) of anhydrous sodium sulphate 3% (parts/vol.) of NaOH 36 B.

1% (parts/vol) of sodium meta-nitro-benzenesulphonate and squeezed until it retains 7 5 of its weight of solution.

This fabric is subsequently steamed for 1 minute at 105 C., thoroughly washed with cold and then with hot water, and finally soaped at the boiling temperature for 20 minutes, and rinsed and dried.

The cotton fabric appears to be dyed in a reddish yellow shade having excellent fastness to washing.

EXAMPLE 22 2 parts of the dyestuif prepared according to Example 6 are dissolved in 2000 parts of distilled water at 50- 55 C.

Into the thus obtained bath, 100 parts of cotton in the form of skeins are immersed and the dyeing is begun, while stirring intermittently.

After 20 minutes from the start, 80 parts of anhydrous sodium sulphate are added at a temperature of 60 C., and after a further 20 minutes, with the bath brought to a temperature of 70 C., the addition is completed with 120 parts of anhydrous Na SO The temperature of the bath is brought to 80 C. in 10 minutes and in two times, in a total period of 20 minutes, 300 parts of an Na CO solution, having a concentration of 10%, are introduced.

The dyeing is continued at a temperature of 80-85" C. for further 60 minutes.

Then the skeins are removed from the dyeing bath, rinsed with cold water and soaped for 30 minutes at the boiling temperature in a solution having a concentration of 3% of Marseille soap, by goods/ bath ratio of 1:50.

The cotton appears to be dyed in a violet-brown shade having excellent fastness to wet treatments.

EXAMPLE 23 2 parts of the dyestuif prepared according to Example 10, mixed with 2 parts of NaCO and 20 parts of urea, are dissolved in parts of water.

A cotton fabric is impregnated with the thus obtained solution, squeezed until it retains 75 by weight of the liquid, and dried until the material still contains about 15% of residual moisture. Subsequently the fabric is subjected to the action of dry heat for 5 minutes at a temperature comprised between -160 C., rinsed first with cold and then with hot water, and soaped for 15-20 minutes in a solution of nonionic surfactant having a concentration of 0.3%.

It is rinsed once more and then dried.

A fabric dyed in a brillant turquoise blue shade having good fastness is obtained.

EXAMPLE 24 A printing paste of the following composition is prepared:

The paste is applied to a mercerized cotton fabric.

The fabric is dried and steamed for 10 minutes. The printing is then washed in running water for 15 minutes and soaped with an aqueous solution containing 2 g./l. of soap, for 10 minutes at the boiling temperature.

It is rinsed and dried.

The intense blue printing thus obtained has very good fastness to washing and to light.

While the present invention has been described with respect to specific examples, it is to be understood that these examples are for purposes of illustration and that the invention is not limited thereto, since many variations and modifications can be practiced without departing from its spirit and scope.

2. The dyestuff of claim 1 having the structure SOzNa BO NB 3. The dyestufi of claim 1 having the structure NBOxB SOaNa Having described the invention, what it is desired to secure and claim by Letters Patent is:

1. Reactive triazine dyestuff of the formula wherein n is an integer from 2 to 4, the azo dyestutf being a phenyl-azo-naphthyl or pheny l-azo-pyrazolone dyestufl, said azo dyestufi being bonded to the -NH-- group directly through a phenyl or naphthyl radical of said azo dyestutf.

4. The dyestufi of claim 1 having the structure soaNa SOzNa 5. The dyestufi of claim 1 having the structure I Cl SOaNa OaNQ SOaNa 7. The dyestutf of claim 1 having the structure SOaNa 3,429,870 19 20 8. The dyestufi of claim 1 having the structure I III-CH: (3H1 SOaNa Referelices Cited UNITED STATES PATENTS 2,424,493 7/1947 Miillel et a] 260-163 2,769,806 11/1956 Weber 260-182 FOREIGN PATENTS 901,434 7/1962 Great Britain.

CHARLES B. PARKER, Primary Examiner.

D. M. PAPUGA, Assistant Examiner.

US. Cl. X.R.